CN104910776B - A kind of transparent wear super hydrophobic coating and preparation method thereof and coating processes - Google Patents
A kind of transparent wear super hydrophobic coating and preparation method thereof and coating processes Download PDFInfo
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- CN104910776B CN104910776B CN201510280756.0A CN201510280756A CN104910776B CN 104910776 B CN104910776 B CN 104910776B CN 201510280756 A CN201510280756 A CN 201510280756A CN 104910776 B CN104910776 B CN 104910776B
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Abstract
The present invention relates to a kind of transparent wear super hydrophobic coating and preparation method thereof and coating processes.The transparent wear super hydrophobic coating includes nano material dispersion liquid and binding material dispersion liquid.During preparation, by the scattered obtained nano material dispersion liquid of nano material and volatile solvent；Binding material is mixed to scattered obtained binding material dispersion liquid with its good solvent.During coating, first substrate surface is cleaned clean, it is then coated with binding material dispersion liquid and forms tack coat, coated with nano material dispersion liquid after drying, nano material is set to be partially submerged into tack coat by the mode such as heat, pressurize again, the finally nano particle using scraping or the combination of adhesive tape sticky removing loosely, obtains super-hydrophobic coat, the coating translucency is good, adhesion is strong, wear-resisting.The super hydrophobic coating can be used for the surfaces of various materials such as metal, plastics, glass, cement plate, obtain the function such as waterproof, antifouling, anti-corrosion, self-cleaning, anti-dew, anti-icing.
Description
Technical field
The invention belongs to the preparation of super hydrophobic surface and applied technical field, and in particular to a kind of super-hydrophobic painting of transparent wear
Material and preparation method thereof and coating processes.
Background technology
Super-hydrophobic phenomenon is widespread in nature, and such as lotus leaf, butterfly's wing, water skipper leg show excellent super thin
Water-based energy.Structure of the super-hydrophobic coat by micro-nano-scale and the surface with low-surface-energy collectively form, and have the static state of water
Contact angle is more than 150 ° and characteristic of the roll angle less than 10 °.The correlative study of super hydrophobic surface is international scientific in the late two decades
One of the forward position of research and focus, have the function such as self-cleaning, anti-corrosion, drag reduction, waterproof, oleophobic, antifog, anti-ice surface design and
Interfacial characteristics has achieved breakthrough.For example orderly micron post of common super-drainage structure, loose structure, nano wire, micro-nano
Rice corpuscles cluster etc. is respectively provided with phenomena such as scattered color, diffraction to visible ray, therefore the coating prepared is poor into milky, transparency.
In addition to all excellent specific properties with common super hydrophobic surface, transparent hydrophobic surface also ensures the permeability of light, so as to
The performance of relevant device and product is obviously improved, it is more in photovoltaic apparatus, building, automobile, electronic manufacture and textile etc.
Individual field shows the prospect of being widely applied.Research shows that the construction unit of super-drainage structure is less than 200nm, will effectively drop
Low optical dissipates color, it is possible thereby to improve the transparency of coating.But the problem of thus bringing is construction unit and the contact surface of substrate
Product diminishes, and adhesion between the two reduces, and causes hydrophobic structure easy to fall off.To this conventional combination for improving hydrophobic structure and substrate
The method of power is that binding material is coated in structure using the methods of vapour deposition, high-temperature heat treatment and sol-gel.Mesh
Before, transparent hydrophobic surface still fails to realize extensive preparation and business application, mainly in inexpensive, simple and efficient system
Many problems be present in standby technology, coating abrasion performance, durability etc..
The content of the invention
The technical problem of solution：The purpose of the present invention is overcome the deficiencies in the prior art and to provide a kind of transparent wear super thin
Water paint and preparation method thereof and coating processes, to realize that coating is super-hydrophobic, translucency is good, wearability is good and adhesion is strong.
Technical scheme：
A kind of transparent wear super hydrophobic coating, including nano material dispersion liquid and binding material dispersion liquid, wherein nanometer material
Expect the mixed solution that dispersion liquid is nano material and volatile solvent, binding material dispersion liquid is binding material and its good solvent
Mixed solution.
The nano material is hydrophobic gas phase nano silica or dewatering nano silicon dioxide aerosol powder, particle chi
Very little is 20-100nm, and the cluster size being made up of particle is between 200-2000nm；The volatile solvent is ethanol and isopropyl
One or both of alcohol, when being two kinds of solvent mixing, then the volumn concentration of any one solvent is 1-99%.
The binding material is polyurethane micelle, polystyrene latex, fluorocarbon resin, organic siliconresin, phenolic resin, ring
The one or more of oxygen tree fat or alkyd resin；Its described good solvent is one kind in acetone, dimethylbenzene, ethyl acetate and DMF
Or it is a variety of, when being mixed for multi-solvents, then the volumn concentration of any one solvent is 1-99%.
A kind of preparation method of above-described transparent wear super hydrophobic coating, comprises the following steps：
(1) nano material is added in volatile solvent, 10-90min is handled using stirring and ultrasonic disperse mode, formed
The mass fraction of nano material dispersion liquid, wherein nano material is 0.1-10%；
(2) binding material is mixed with its good solvent, temperature control is formed viscous at 20-50 DEG C, mechanical agitation 30-90min
Material dispersion liquid is tied, the wherein mass fraction of binding material is 5-50%.
, can be direct after nano material and volatile solvent are scattered in step (1) in above-described preparation method
Using or add account for dispersion mass fraction be 0.1-10% chain nano silicon, nanometer silica line, carbon
One or more in nanotube, nanometer titanium dioxide silica fibre and zinc oxide nanowire, it is ultrasonically treated 1h；
In step (2) binding material mixed with its good solvent it is scattered after, can be used directly or add and account for dispersion
One or more in polypropylene, polyethylene, Kynoar, silica and aluminum oxide that mass fraction is 0.1-10%,
Size continues to stir 0.5h between 50-100 μm.
A kind of coating processes of above-described transparent wear super hydrophobic coating, comprise the following steps：
As shown in figure 1, matrix surface to be coated is subjected to dust removal, degreasing processing until clean；Then by binding material
Dispersion liquid is sprayed or brushed forms tack coat on matrix surface, and its thickness control places drying after 0.5-20 μm, coating；So
Coated with nano material dispersion liquid afterwards；After drying, to be partially submerged into nano material viscous by the way of pressurization, heating or both combine
Tie layer；Finally utilize plastic plate, rubber film, porous polymer foam or paper handkerchief scratch coating, or with adhesive tape sticky removing, to remove
With reference to coating particles loosely.
Dry condition is placed after the coating for spacious environment, in airspace, by auxiliary blowing device or 30-50 DEG C
At a temperature of, dry 5-120min；
The painting method of the nano material dispersion liquid is：Apart from matrix 15cm, the air cannon for being 60psi with pressure will
Nano material dispersion liquid replaces anyhow, and even application is on dried tack coat.
The pressurization, mode of heating are：Using infrared lamp power 100-1000W or heat gun power 100-5000W to applying
Layer is overall to carry out heating 1-30min；Or
Matrix is positioned in thermal station or baking oven, 40-90 DEG C of temperature, heats 1-30min；Or
Apply mechanical pressure, pressure 0.1- using high pressure air rifle, pressurized metal plate or pressurization glass plate in coating surface
10MPa。
The mode of the scraping is back and forth reciprocating or unidirectional scraping, and it is 1-10 times to scrape number；
The adhesive tape is pressure sensitive adhesive, adhesive tape or line paper self-adhesive tape.
Beneficial effect：
First, after coating of the invention coating, suitable surface roughness and low-surface-energy, therefore obtained painting can be built
Layer has super-hydrophobicity, and the water static contact angle of coating surface is more than 160 °, and roll angle is less than or equal to 5 °, and part can even reach
175 ° of contact angle, 1 ° of roll angle；
Second, due to having selected particle diameter to be less than 200nm nano material in the present invention, therefore effectively reduce optics and dissipate
Color, so as to improve the transparency of coating, translucency is good, is more than 85% in visible wavelength range undercoating transmitance, infrared
Line wave band, light transmittance 105%, there is antireflective effect；
3rd, the coating particles combined loosely are got rid of in of the invention, enhance the wearability of coating；
4th, nano material is partially embedded into tack coat in of the invention, on the premise of transparency is ensured, enhanced
The adhesion of super-drainage structure and substrate, so as to improve the durability of coating.
Brief description of the drawings
Fig. 1 is the coating step schematic diagram of the super hydrophobic coating of the present invention, in figure, 1, matrix；2nd, tack coat；3rd, nanometer
Grain or cluster；
Fig. 2 is the microcosmic schematic diagram on super-hydrophobic coat surface made from super hydrophobic coating of the water droplet in the application present invention；
Fig. 3 is in visible wavelength range, using the transmission of super-hydrophobic coat made from the super hydrophobic coating of the present invention
Rate spectrogram；
Fig. 4 is the surface shape after being wiped 100 times using super-hydrophobic coat paper handkerchief made from the super hydrophobic coating of the present invention
Looks.
Embodiment
Following examples further illustrate present disclosure, but should not be construed as limiting the invention.Without departing substantially from
In the case of spirit and essence of the invention, the modification and replacement made to the inventive method, step or condition, the present invention is belonged to
Scope.Unless otherwise specified, the conventional meanses that technological means used in embodiment is well known to those skilled in the art.
Embodiment 1：
Coating preparation:
0.5g Degussa Aerosil-R972 hydrophobic fumed silica (particle sizes are added into 500mL ethanol solutions
For 20-100nm), stir, be put into ultrasonic cleaner (power 600W) and be ultrasonically treated 10min, produce nano material point
Dispersion liquid；
Under mechanical agitation (300 revs/min of rotating speed), by 50g elastic polyurethane micellesWith 300mL third
The mixed solution of ketone and 200mL dimethylbenzene mixes 30min, produces binding material dispersion liquid.
The transparent wear super hydrophobic coating includes nano material dispersion liquid and binding material dispersion liquid.
Coating processes:
Pure water cleaning panes, the air cannon that obtained binding material dispersion liquid is 40psi with pressure is passed through into spraying
It is sprayed on glass plate (15*15cm2, thickness 15mm) on, then thickness control is placed on doing in ventilating kitchen at 0.5 μm
Dry 30min, after the completion of drying, apart from glass plate 15cm, the nano material prepared is disperseed with the air cannon that pressure is 60psi
Liquid replaces anyhow, and even application is positioned in 50 DEG C of baking oven on dried glass plate and heats 15min, finally with U.S. line
Adhesive tape sticky removing combines coating particles loosely.
The super-hydrophobicity and anti-wear performance of glass plate after test coating, test result is that the static contact angle of coating is
169 °, roll angle is 3 °, and (heavy burden 10N/100mm is tested through polishing2, polish 200 times, rotating speed 100r/min) after, Static Contact
Angle is 155 °, and roll angle is 5 °, and Fig. 3 is the transmitance spectrogram of the coating.
Embodiment 2：
Coating preparation:
50g Jis are added into 500mL aqueous isopropanols must contain HL-150 hydrophobic fumed silicas (particle size 20-
100nm), stir, be put into ultrasonic cleaner (power 600W) and be ultrasonically treated 90min, produce nano material dispersion liquid；
Under mechanical agitation (300 revs/min of rotating speed), by 50g elastic polyurethanesIt is molten with 500mL acetone
After liquid stirring 30min, 5g polypropylene (particle diameter is 100 μm) is added thereto, continues to stir 0.5h, produces binding material and disperse
Liquid.
The transparent wear super hydrophobic coating includes nano material dispersion liquid and binding material dispersion liquid.
Coating processes:
Pure water cleaning panes, the air cannon that obtained binding material dispersion liquid is 40psi with pressure is passed through into spraying
It is sprayed on glass plate (15*15cm2, thickness 15mm) on, then thickness control is placed on drying in ventilating kitchen at 5 μm
60min, after the completion of drying, apart from glass plate 15cm, the nano material dispersion liquid that will be prepared with the air cannon that pressure is 60psi
Vertical and horizontal alternating, even application after the completion of to be dried, apply 1MPa pressure with pressurized metal plate on dried glass plate
2h, the coating particles combined loosely are finally removed with adhesive tape.
The super-hydrophobicity and anti-wear performance of glass plate after test coating, test result is that the static contact angle of coating is
169 °, roll angle is 3 °, and (heavy burden 10N/100mm is tested through polishing2, polish 200 times, rotating speed 100r/min) after, Static Contact
Angle is 157 °, and roll angle is 4 °, and Fig. 4 is the surface topography after the coating paper handkerchief wipes 100 times.
Embodiment 3：
Coating preparation:
20g dewatering nano silicon dioxide aerosol powders (particle size 20- is added into 500mL ethanol solutions
100nm), stir, be put into ultrasonic cleaner (power 600W) and be ultrasonically treated 60min, then add 5g chain nanometers
Silica, it is put into ultrasonic cleaner (power 600W) and is ultrasonically treated 1h, produce nano material dispersion liquid；
Under mechanical agitation (300 revs/min of rotating speed) and 50 DEG C of waters bath with thermostatic control, by 25g France A Kema 28-800EVA and
500mL xylene solutions stir 90min, produce binding material dispersion liquid.
The transparent wear super hydrophobic coating includes nano material dispersion liquid and binding material dispersion liquid.
Coating processes:
Cement plate alkali lye is cleaned, and obtained binding material dispersion liquid is brushed in cement plate (24*12cm2, thickness 25mm)
On, then thickness control is placed on drying 1h in ventilating kitchen at 10 μm, after the completion of drying, the air for being 60psi with pressure
Rifle, apart from cement plate 15cm, the nano material dispersion liquid prepared is replaced anyhow, even application is in dried cement plate
On, 20min is integrally then heated to coating with the heat gun that power is 500W, the painting combined loosely is finally removed with masking tape
Expect particle.
The super-hydrophobicity and anti-wear performance of cement plate after test coating, test result is that the static contact angle of coating is
170 °, roll angle is 3 °, and (heavy burden 10N/100mm is tested through polishing2, polish 200 times, rotating speed 100r/min) after, Static Contact
Angle is 159, and roll angle is 5 °.
Embodiment 4：
Coating preparation:
5g Degussa Aerosil-R972 hydrophobic fumed silicas are added into 500mL ethanol solutions, and (particle size is
20-100nm), stir, be put into ultrasonic cleaner (power 600W) and be ultrasonically treated 60min, then add 50g carbon and receive
Mitron, it is put into ultrasonic cleaner (power 600W) and is ultrasonically treated 1h, produce nano material dispersion liquid；
Under mechanical agitation (300 revs/min of rotating speed) and 50 DEG C of waters bath with thermostatic control, by 25g France A Kema 28-800EVA and
500mL xylene solutions stir 90min, add 5g aluminum oxide (particle diameter is 50 μm), stir 0.5h, produce binding material and disperse
Liquid.
The transparent wear super hydrophobic coating includes nano material dispersion liquid and binding material dispersion liquid.
Coating processes:
Cement plate alkali lye is cleaned, and obtained binding material dispersion liquid is brushed in cement plate (24*12cm2, thickness 25mm)
On, then thickness control is placed on drying 1h in ventilating kitchen at 20 μm, after the completion of drying, the air for being 60psi with pressure
Rifle, apart from cement plate 15cm, the nano material dispersion liquid prepared is replaced anyhow, even application is in dried cement plate
On, it is positioned in 60 DEG C of baking oven and dries 15min, the coating particles combined loosely is finally removed with masking tape.
The super-hydrophobicity and anti-wear performance of cement plate after test coating, test result is that the static contact angle of coating is
169 °, roll angle is 3 °, and (heavy burden 10N/100mm is tested through polishing2, polish 200 times, rotating speed 100r/min) after, Static Contact
Angle is 158, and roll angle is 5 °, and its microcosmic schematic diagram is as shown in Figure 2.
Claims (8)
- A kind of 1. transparent wear super hydrophobic coating, it is characterised in that including nano material dispersion liquid and binding material dispersion liquid, its Middle nano material dispersion liquid be 0.1-10 mass % nano material and volatile solvent mixed solution, binding material dispersion liquid The mixed solution of the good solvent of binding material and the binding material for 5-50 mass %；The nano material is hydrophobic gas phase nano silica or dewatering nano silicon dioxide aerosol powder, particle size are 20-100nm, the cluster size being made up of particle is between 200-2000nm；The binding material is polyurethane micelle, polystyrene latex, fluorocarbon resin, organic siliconresin, phenolic resin, asphalt mixtures modified by epoxy resin Fat or alkyd resin, and the binding material dispersion liquid is further 0.1-10 mass % comprising dispersion mass fraction is accounted for One kind or more in the polypropylene between 50-100 μm, polyethylene, Kynoar, silica and aluminum oxide of size Kind.
- 2. a kind of transparent wear super hydrophobic coating according to claim 1, it is characterised in that the volatile solvent is second One or both of alcohol and isopropanol, when being two kinds of solvent mixing, then the volumn concentration of any one solvent is 1- 99%.
- A kind of 3. transparent wear super hydrophobic coating according to claim 1, it is characterised in that the binding material it is good molten Agent is the one or more in acetone, dimethylbenzene, ethyl acetate and DMF, for multi-solvents mixing when, then any one solvent Volumn concentration is 1-99%.
- A kind of 4. preparation method of transparent wear super hydrophobic coating according to claim any one of 1-3, it is characterised in that Comprise the following steps：(1) nano material is added in volatile solvent, 10-90min is handled using stirring and ultrasonic disperse mode, forms nanometer Material dispersion liquid；(2) binding material is mixed with the good solvent of the binding material, temperature control is at 20-50 DEG C, mechanical agitation 30- 90min, then, add account for size of the dispersion mass fraction for 0.1-10 mass % between 50-100 μm poly- third One or more in alkene, polyethylene, Kynoar, silica and aluminum oxide, continue to stir 0.5h, form binding material Dispersion liquid.
- 5. the preparation method of a kind of transparent wear super hydrophobic coating according to claim 4, it is characterised in that in step (1) after nano material and volatile solvent are scattered in, the chain for accounting for that dispersion mass fraction is 0.1-10% is added Nano silicon, nanometer silica line, CNT, nanometer titanium dioxide silica fibre and one kind in zinc oxide nanowire or It is a variety of, it is ultrasonically treated 1h.
- A kind of 6. coating processes of transparent wear super hydrophobic coating according to claim any one of 1-3, it is characterised in that Comprise the following steps：Matrix surface to be coated is subjected to dust removal, degreasing processing until clean；Then binding material dispersion liquid is sprayed or brushed It is coated on matrix surface and forms tack coat, its thickness control places drying after 0.5-20 μm, coating；It is then coated with nano material Dispersion liquid；After drying, nano material is set to be partially submerged into tack coat by the way of pressurization, heating or both combine；Finally utilize Plastic plate, rubber film, porous polymer foam or paper handkerchief scratch coating, or with adhesive tape sticky removing, to remove the painting combined loosely Expect particle.
- A kind of 7. coating processes of transparent wear super hydrophobic coating according to claim 6, it is characterised in that the coating Dry condition is placed afterwards in spacious environment, airspace, by auxiliary blowing device or at a temperature of 30-50 DEG C, to dry 5- 120min；The painting method of the nano material dispersion liquid is：Apart from matrix 15cm, the air cannon for being 60psi with pressure, by nanometer Material dispersion liquid replaces anyhow, and even application is on dried tack coat；The mode of the scraping is back and forth reciprocating or unidirectional scraping, and it is 1-10 times to scrape number；The adhesive tape is pressure sensitive adhesive, adhesive tape or line paper self-adhesive tape.
- 8. the coating processes of a kind of transparent wear super hydrophobic coating according to claim 6, it is characterised in that described to add Pressure, mode of heating are：Coating is integrally heated using infrared lamp power 100-1000W or heat gun power 100-5000W 1-30min；OrMatrix is positioned in thermal station or baking oven, 40-90 DEG C of temperature, heats 1-30min；OrApply mechanical pressure, pressure 0.1- using high pressure air rifle, pressurized metal plate or pressurization glass plate in coating surface 10MPa。
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| US9056987B2 (en) * | 2013-01-30 | 2015-06-16 | Illinois Tool Works, Inc. | Super hydrophobic coating |
| CN103788802B (en) * | 2014-01-08 | 2017-01-04 | 深圳大学 | A kind of preparation method of super-hydrophobic coat |
| CN104017440B (en) * | 2014-05-23 | 2016-04-27 | 中国人民武装警察部队杭州士官学校 | Preparation method of a kind of super hydrophobic coating and products thereof and application |
| CN104231916B (en) * | 2014-09-30 | 2016-08-24 | 东南大学 | A kind of transparent hydrophobic nano coating and spraying preparation method thereof |
| CN104449357B (en) * | 2014-11-26 | 2017-01-04 | 浙江大学 | A kind of transparent hydrophobic coating material and the method preparing transparent hydrophobic coating thereof |
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